Addition polymers of ethylenically-unsaturated cyclic nitrile sulfites,carbonates and oxalates



United States Patent 3,480,595 ADDITION POLYMERS OF ETHYLENICALLY-UN-SATURATED CYCLIC NITRILE SULFITES, CAR- BONATES AND OXALATES Emmett H.Burk, Jr., Glenwood, 11]., and Donald D. Carlos, Crown Point, Ind.,assignors to Sinclair Research, Inc., New York, N.Y., a corporation ofDelaware No Drawing. Continuation-impart of application Ser. No.592,285, Nov. 7, 1966. This application Nov. 9, 1967, Ser. No. 681,925

Int. Cl. C08f 19/18; C08g 33/00 US. Cl. 260-77.5 13 Claims ABSTRACT OFTHE DISCLOSURE The disclosure is of ethylenically-unsaturated cyclicnitrile compounds of the formula /X ((l) O O O 1.2. galzl wherein X is athionyl, carbonyl or oxalyl group, Y is an addition polymerizable,ethylenically unsaturated group (e.g., vinyl), and x is 0 or 1. Thecompounds may be polymerized to form homopolymers or addition polymerswith ethylenically-unsaturated polymerizable monomers (e.g. styrene).

wherein X is a thionyl,

II ll 0 li -S, carbonyl, C, or oxalyl, -C-C group, x is 0 or 1, and Y isan ethylenically unsaturated hydrocarbon group, usually of 2 to about20, or 2 to about 12, carbon atoms. The Y group is essentiallyhydrocarbonaceous, this term being intended to include hydrocarbonswhich are substituted with non-deleterious substituents, for example,chlorine or bromine. When free of aromatic substituents, Y preferablyhas 2 to about 6 carbon atoms; when containing aromatic substituents, Ypreferably has 8 to about 12 carbon atoms. The Y group may be poly-, forexample, di, as well as mono-, ethylenically-unsaturated. When x is 0,it is often preferred that the ethylenic group, C=C be a terminalethylenic group, i.e., CH =C As specific examples of suitable Y groupsfor the adducts of the present invention may be mentioned vinyl,vinylidene or vinylene hydrocarbon groups, preferably of 2 to 20 carbonatoms, such as for instance, ,rnonoand di-alphaolefinic groups such asvinyl, l-pentenyl, I-octenyl, 1,4-butadienyl and isoprenyl groups andvinyl, vinylidene or vinylene aromatic groups such as, for instance,

styrenyl, alpha-, ortho-, metaand para-methylstyrenyl groups,divinylbenzenyl groups, etc. Thus, illustrative of the cyclic compoundsof the invention when named as nitrile derivatives are, for example,acrylonitrile oxalate, acrylonitrile carbonate, p-vinyl benzonitrilecarbonate, fumaronitrile dicarbonate, methacrylonitrile oxalate,fumaronitrile disulfite, crotononitrile carbonate, mesacononitriledicarbonate, etc.

Ethylenically-unsaturated cyclic nitrile adducts of the presentinvention are useful, for instance, as precursors for preparing thecorresponding ethylenically'unsaturated isocyanates and asaddition-polymerizable monomers for the preparation of cyclicnitrile-containing polymers, which polymers are, in turn, useful asprecursors for the corresponding isocyanate-containing polymers. 'Ingeneral, the cyclic nitrile sulfite ring is less stable than the nitrileoxalate group, the latter being less stable than the nitrile carbonategroup. As a result the nitrile sulfite adducts are usually less suitablefor making polymers, especially if it is desired to keep the cyclicnitrile sulfite ring intact during polymerization, but these nitrilesulfites are readily decomposed by heat to the corresponding unsaturatedisocyanates. On the other hand the nitrile carbonates can be difficultto thermally decompose to isocyanates.

Thus, for example, the cyclic nitrile sulfite adducts of the inventioncan, by the application of heat, be converted to the corresponding,ethylenically-unsaturated isocyamates with S0 being evolved in thereaction. Paravinyl benzonitrile sulfite, for instance, when. heated toabout C. is converted to p-vinylphenylisocyanate. Similarly, the cyclicnitrile oxalate adducts, when heated, generate the corresponding,unsaturated isocyanates with CO and CO being evolved, or these oxalateadducts may first be addition polymerized to form polymeric precursorsof polymeric isocyanates. Finally, the cyclic nitrile carbonate adductsof the invention may likewise be addition polymerized to yield cyclicnitrile carbonate-containing polymers.

The molecular weight of the cyclic nitrile adductderived addition typepolymers of the present invention may vary widely as, for instance, fromabout 2 50 or 750 to about 20,000 or 500,000 or more, often about 750 to200,000. As aforementioned, the polymers may be homopolymers, in whichcase the cyclic nitrile adduct-derived groups repeat in a regularfashion, or polymers of the cyclic nitrile adduct and at least onedissimilar ethylenically-unsaturated monomer. In the latter case, thepolymers may be regular, random, block or graft, at least 1 to 99% byWeight of which being composed of the cyclic nitrile adduct-derivedmonomer with the balance 99 to 1% being composed of one or moredissimilar ethylenically-unsaturated monomers. Often preferred polymersare those wherein about 5 to 25 weight percent of the monomers iscomposed of the cyclic nitrile adduct.

By dissimilar, ethylenically-unsaturated monomers is meant monomerswhich are different. from the cyclic nitrile adduct monomers of theinvention, that is, which fall outside the definition of the class ofcyclic nitrile adducts described herein. Suitable such dissimilarmonomers which may be reacted with the polymerizable cyclic nitrileadducts to form polymers of the present invention are chemically stableunder the conditions employed for addition polymerization and have nogroups which react with the cyclic nitrile groups of the adducts undersuch conditions. These dissimilar monomers are additionpolymerizable dueto their being at least mono-ethylenically-unsaturated. The dissimilarmonomer usually contains 2 to about 20 carbon atoms, and often preferredare those monomers having a terminal ethylenic group, i.e. CH =CSuitable dissimilar monomers include vinyl hydrocarbons such as, forinstance, monoand di-alpha olefins such as ethylene, l-octene, butadieneand isoprene; styrene, alpha-, ortho-, metaand para-methylstyrenes, thedivinyl benzenes, etc.; the acrylic type acids, nitriles, amides andesters; the allylic-type carboxylic esters and alcohols; tl-iemonovinylpyridines; n-vinyl pyrrolidone, vinylidene monomers; vinylesters of carboxylic acids; vinyl halides; the alkyl vinyl ethers; thealkyl vinyl ketones; alkylene dicarboxylic acids and anhydrides, etc.

Some acrylic type compounds may have the structure:

Q RCH==(EZ wherein Q is hydrogen, halogen or a hydrocarbon radical, sayof 1 to 12 carbon atoms, as, for instance, alkyl, alkenyl, cycloalkyl,aryl and aralkyl and Z is selected from CN, -COOR and -CON wherein R ishydrogen or a hydrocarbon radical as defined in Q above. Importantmonomers of this type include acrylonitrile and the ethylacrylates,including the lower alkylmethacrylates.

Allylic-type esters and acids include those having the structure:

Q! (CH2=J3-CH2)nY wherein Q is hydrogen, halogen,

ll CR, COR

or a hydrocarbon radical of l to 12 carbon atoms, preferably alkyl oraryl; n is 1 to 2; Y is it i -ooR" or OOR when n is l, and a diacyloxyradical of a carboxylic acid when n is 2. R" in the radicals ll ll OCRand -COR" may be hydrogen or a hydrocarbon radical such as an alkyl,alkenyl, cycloalkyl, aryl or aralkyl, usually of 2 to 12 carbon atoms.Representative monomers of this type are di(methallyl) succinate, allylacetate, diallyl phthalate and dimethyl itaconate.

Monovinylpyridines include vinylpyridines, viz., the 2- vinyl-,3-vinyland 4-vinylpyridines, and the alkylsubstituted vinylpyridines,e.g., 2-methyl-5-vinylpyridine, and the like. N-vinyl monomers includeN-vinylpyrrole, N-vinyl carbazole, N-vinylindole, N-vinylsuccinimide andthe like.

Vinyl compounds include those having the structure CH CHA where A ishalogen or an acyloxy radical as for instance vinyl chloride and vinylacetate. Vinylidm e monomers include, for example, vinylidinedichloride, dracetate, dinitrile and the like. Illustrative of suitablealkylene dicarboxylic acids and anhydrides are maleic, gluconic amdallylrnalonic acids and anhydrides.

The novel polymers of the invention may be solid or liquid and can beprepared by known polymerization processes such as solution, bulk andemulsion processes. Solution polymerization in a suitable solvent,employing as a polymerization catalyst a free-radical initiator, such asa peroxide or an azo-type catalyst, is preferred. Suitable solvents forsolution polymerization include aromatic hydrocarbon solvents such asbenzene, cumene, xylene, toluene, etc. Some examples of free-radicalpolymerization catalysts are benzoyl peroxide, dicumyl peroxide,azoisobutyronitrile, alpha,alpha-azodiisobutyronitrile, etc.

The polymerization is often carried out at a temperature below thedecomposition temperature of the ring of the cyclic nitrile adductcompound employed but such decomposition may be etfected duringpolymerization if desired or if not deleterious. In general, thepolymeriza tion can be performed at temperatures of about 50 to C., andadvantageously the temperatures can be about 70 to 90 C.

The polymers of the present invention are valuable intermediates orprecursors for the preparation of organic foams, elastomers, dryingoils, etc. As mentioned earlier, for example, the polymers can bethermally decomposed to polyisocyanates which may be reacted orcrosslinked, for instance, with diamines or diols, to give thermosettingmaterials. These polyisocyanates may also be used as plasticizers or inthe preparation of urethane coatings, adhesives, sealants, etc. The newpolymers of the present invention can also be hydrolyzed to hydroxamicacids.

An additional feature of the polymers of the invention is that they maybe reacted with polyamines or polyols to provide polyhydroxamates whichare the subject of copending application Ser. No. 592,288 filed Nov. 7,1966. Reaction of the cyclic nitrile adduct group-containing polymers ofthe invention with polyols produces thermoplastic materials containing acertain hydroxamate as cross-links, described in the above copendingapplication Ser. No. 592,288, between polymer chains, which crosslinksare thermally unstable and break down with mild heating to isocyanategroups and the corresponding polyol. The resulting polymeric material isthen easily molded, after which crosslinks again reform by reaction ofthe isocyanate and polyol to give a thermoset material. Thus, the novelhydroxamates provide a method of making molded objects from thermosetmaterials such as crosslinked polyurethanes without resorting to therelatively high temperatures ordinarily required to render crosslinkedpolyurethanes moldable and, therefore, without the product degradationthat often accompanies the use of such high temperatures.

Another advantage of the polymers of the invention resides in the factthat they contain an internal or built in blowing agent in theirstructure, that is, the carbon dioxide and carbon monoxide they evolveupon decomposition. This feature can be utilized in the preparation oforganic foams such as polyurethane foams. The ability of the polymers ofthe invention to generate polyisocyanates upon heating provides anadditional advantage in that the polymers of the invention, in contrastto isocyanates, are stable in the absence of water and therefore can behandled and stored.

Decomposition of certain of the polymers to the correspondingpolyisocyanates can be effected by heating the polymers to a temperaturebelow the degradation point of the desired polyisocyanate product. Theheating temperature employed will vary, of course, depending upon thedecomposition temperature of the feed and degradation temperature of theparticular polyisocyanate being prepared. In most cases, however,temperatures will usually fall in the range of about 50 to 200 C.,preferably about 75 to C. Advantageously, the decomposition is conductedin the presence of an inert solvent such as benzene, xylene, toluene,chlorobenzene and the like.

The cyclic nitrile adduct monomers of the invention can be prepared byreacting the appropriate hydroxamic acid and acid chloride. For example,vinyl benzonitrile sulfite can be prepared by reacting vinylbenzohydroxamic acid with thionyl chloride. Hydroxamic acids which reactwith thionyl chloride, oxalyl chloride and phosgene to produce thenitrile monomers can be represented by-the structure:

wherein Y is as defined above in the structure of the nitrile monomers.

The temperature for affecting the reaction of the hydroxamic acid andacid chloride may vary depending upon the particular hydroxamic acidselected but in all cases should be conducted below the decompositiontemperature of the desired nitrile monomer. Reflux temperatures can alsobe used as long as the reflux temperature of the particular mixture isbelow the decomposition temperature of the corresponding nitrile monomerproduced. The reaction temperature will often fall in the range of up toabout 90 C., preferably up to about 50 C., when preparing aromaticnitrile monomers and often up to about 40 C. or 70 C., preferably up toabout 30 C., when preparing aliphatic nitrile monomers. The reaction canbe successfully run at temperatures as low as about -30 C. Ordinarilythe reaction will proceed readily at atmospheric pressure but subandsuperatmospheric pressure can be employed if desired. The acid chloridereactant can be in excess and a large excess of acid chloride isparticularly preferred. The reaction can be conducted in the liquidphase and in many cases the hydroxamic acid will react from the solidstate. Advantageously, the hydroxamic acid is first dissolved orslurried in aromatic hydrocarbons, halogenated aliphatic hydrocarbons oran oxygen-containing organic solvent. Illustrative of suitable solventsare the acid chloride reactant itself and normally liquid organicmaterials such as chloroform, benzene, toluene, ethers, esters, furans,dioxanes, and the like. A preferred solvent is the acid chloridereactant, an excess of which will partially dissolve the hydroxamicacid.

The reaction is often over in less than about 0.5 hour, for example,within 15 minutes, or in about 5 to 20 hours, depending upon thereaction temperature employed, and is marked by a cessation in hydrogenchloride gas evolution. Normally at least about 0.5 hour is required forthe reaction to go to completion at temperatures which minimize sidereactions. The reaction is usually quite rapid as the hydroxamic acid isdissolved. At the lower reaction temperatures the hydroxamic acid isgenerally slow to dissolve and may even come out of solution, go backinto solution, etc., during the reaction.

The nitrile monomer can be recovered from the resulting solution by anydesirable means, for instance, by first filtering the resulting solutionto remove any unreacted starting materials and subjecting the filtrateto reduced pressure to remove unreacted acid chloride and inert solvent,if employed, and provide the nitrile monomer as a crude product.Alternately, prior to the filtering step, the solution can be cooled tocrystallize out the product and the product then recovered as described.The crude product, which can be either crystalline or liquid, dependingon the particular nitrile monomer prepared, contains small amounts ofimpurities high in chlorine content. A purer product, essentiallychlorine-free, can be obtained by recrystallization techniques, as, forinstance, from a suitable solvent such as ether, pentane,dichloromethane, carbon disulfide, ethyl acetate, acid chloride and thelike, and mixtures thereof.

A convenient method for obtaining an essentially chlorine-free nitrilemonomer is by extraction or washing with a hydrocarbon solvent. Anynormally liquid hydrocarbon solvent can be used for the extraction as,for instance, alkanes of 5 to 15 or more carbon atoms, aromatic solventssuch as benzene, xylenes, toluene, chlorobenzene and the like. A minimumamount of solvent is w is by initially reacting hydroxylamine and analiphatic lactone to form an aliphatic hydroxamic acid having a hydroxylsubstituent on the aliphatic chain. The hydroxamic acid is then reactedwith an excess of phosgene to convert the alcohol portion to achloroformate and the hydroxamic acid portion to the cyclic nitrilecarbonate. Reaction of the cyclic nitrile chloroforrnate and a strongbase, for example, a strong tertiary amine, gives a nitrile .adductmonomer having the desired polymerizable, ethylenically-unsaturated Ysubstituent.

The above reactions may be represented by the following generalequations, wherein R is alkylene of l to 3 carbon atoms, R is hydrogenor hydrocarbyl, e.g., lower alkyl. and n is 0 or 1:

The aliphatic lactone reacted with hydroxylamine can have 4 to 7 membersin the ring and may be substituted with, for example, lower alkylgroups, provided that the lactone contains at least one hydrogen atomattached to a carbon atom (whether pendant or in the ring) which isadjacent to the carbon atom which forms an ester linkage With the ringoxygen. By way of explanation, in the formula:

that carbon which is indicated by the asterisk is considered the carbonatom which forms an ester linkage with the oxygen. Adjacent thereto mustbe another carbon atom (not shown) having at least one hydrogen atomattached to it. As examples of suitable aliphatic lactones there may bementioned, then, B-propriolactone, fi-isobutyrolactone,,B-isovalerolactone, on isocrotonolactone, caprolactone, etc.

" The preferred lactones suitable for use as starting materials in themethod are lactones which give polymerizable, aliphatic,ethylenically-unsaturated cyclic nitrile carbonates wherein theethylenic unsaturation is conjugated to the nitrile group, such as, forexample, acrylonitrile carbonate. Thus, some examples of the preferredlactones are p-propriolactone, fi-isobutyrolactone, fi-isovalerolactone,etc.

The reaction of the lactone and hydroxylamine (Equation 1, above) can beeffected by combining the reactants in the presence of a suitablesolvent for the hydroxylamine, for example, tetrahydrofuran, ether,methanol, etc., at temperatures below the decomposition temperature ofthe hydroxylamine, say about 10 to 70 C., preferably about -5 C. to 30C. The hydroxy-aliphatic hydroxamic acid product can be precipitatedfrom admixture with an organic solvent by the addition of, for example,chloroform, and recovered by filtration. Should the reaction beconducted in water, the product can be recovered by removal of waterunder reduced pressure.

I In the reaction of phosgene and the hydroxy-aliphatic hydroxamic acid(Equation 2), the amount of the phosgene employed is preferably inexcess of the stoichiometric amount. The reaction temperature should bekept below that at which the chlorine of the chloroformate reacts, forinstance, at a temperature below about C., for example, in the range ofabout 5 to 5 C. If it is desired to employ a solvent for the hydroxamicacid, solvents which do not react with phosgene, for example,hydrocarbon solvents, chlorinated hydrocarbons, etc., should beemployed. To hasten the reaction of the hydroxy-aliphatic hydroxamicacid and phosgene, a weakly basic material which is unreactive towardsthe chloroformate product, for instance, dimethylaniline, may be addedto combine with the HCl produced in the reaction and provide asubstantial absence of free HCl in the reaction mixture. An excess ofthe basic material should be avoided since it later is removed from theproduct. After removal of volatiles, for example, excess phosgene,solvent, etc., the desired cyclic nitrile chloroformate can berecovered.

Decarboxylation-dehydrohalogenation of the cyclic nitrile chloroformateto give a cyclic nitrile adduct monomer having the desiredpolymerizable, ethylenically-unsaturated aliphatic substituent (Equation3) can be effected by treating the cyclic nitrile chloroformate with astrong tertiary aliphatic amine such as triethylamine. The exothermicreaction is conducted at a rate such that a temperature preferably inthe range of about to 40 C. is maintained. The reaction mixture isseparated by, for example, washing with water to remove the aminehydrochloride and dried. The desired cyclic nitrile adduct monomer canbe recovered by distillation.

The following examples will serve to illustrate the Present inventionbut are not to be considered limiting:

EXAMPLE I Preparation of p-vinylbenzonitrile carbonate A solution of 12g. (0.074 mole) of p-vinylbenzohydroxamic acid and 100 cc. (largeexcess) of phosgene in 75 cc. ether and cc. tetrahydrofuran was allowedto stir at room temperature for half an hour. The reaction mixture wasfiltered and the solvents removed under reduced pressure. Thereresulted, after trituration with pentane, 9.8 g. (70%) ofp-vinyl'benzonitrile carbonate, M.P. 70-72 C.

Analysis.--Calc. for C H NO C, 63.49; H, 3.73; N, 7.41; T, 25.37. Found:C, 64.45; H, 3.99; N, 7.08.

The infrared spectrum of the product (Nujol mull) showed the typicalnitrile carbonate absorptions.

EXAMPLE II Preparation of p-vinylbenzonitrile sulfite To a rapidlystirred mixture of 16.3 g. (0.10 mole) of p-vinylbenzohydroxamic acid in100 cc. ether was added dropwise 23.8 g. (0.20 mole) of thionyl chlorideover a period of half an hour. The reaction mixture was allowed to stirfor another half-hour at room temperature. The resulting solution wasfiltered and the solvents removed under reduced pressure. There wasobtained 19.3 g. (92%) of p-vinylbenzonitrile sulfite, M.P. 56-60" C.Recrystallization from an ether-pentane mixture gave white crystals,M.P. 60-61 C.

8 Analysis-Gale. for C9H7NO3SI C, 51.70; H, 3.35; N, 6.70; O, 22.92; S,15.33. Found: C, 52.23; H, 3.57; S, 15.45.

The infrared spectrum of the product (Nujol mull) showed the typicalnitrile sulfite peaks.

EXAMPLE III Preparation of p-vinylbenzonitrile oxalate To a 20 cc.(large excess) of oxalyl chloride was added in portions 1.0 g. (0.0061mole) of p-vinylbenzohydroxamic acid and the reaction mixture refluxedfor five minutes. The resulting solution was filtered and set asideuntil the product crystallized from solution. There was obtained 0.80 g.(62%) of p-vinylbenzonitrile oxalate, M.P. -147" C.

Analysis.-Calc. for C H NO C, 60.83; H, 3.25; N, 6.45; O, 29.47. Found:C, 60.58; H, 3.42; N, 6.70.

The infrared spectrum of the product (Nujol mull) showed typical nitrileoxalate absorptions.

EXAMPLE IV Preparation of acrylonitrile carbonate (A) Preparation of 8hydroxy propiohydroxamic acid.-To a 3 liter, 3 necked, fluted, roundbottom flask equipped with stirrer, dropping funnel, condensor andthermometer, containing 800 ml. of methanol and 208.5 g. (3 moles) ofhydroxylamine hydrochloride, were added 303 g. (3 moles) oftriethylamine dropwise at room temperature. The slurry was stirredconstantly. After the addition was completed the temperature was takendown to 0 C. and maintained there while 216 g. (3 moles) offl-propiolactone was added dropwise. The reaction mixture was thenallowed to equilibrate to room temperature and O-hydroxypropiohydroxamicacid was precipitated out by adding 2400 ml. of chloroform. Afterstanding in the refrigerator for some hours the crystalline product wasfiltered off, dried at reduced pressure, and 241 g. (77% yield) ofO-hydroxypropiohydroxamic acid, identified by IR. analysis and meltingpoint was recovered.

(B) Preparation of 2-(nitrile carbonato) ethyl chlorof0rmate.The set-updescribed in step I containing 900 ml. of chloroform and g. (1.42 moles)of fl-hydroxypropiohydroxamic acid, was charged with 350 g. (3.56 moles)of phosgene. The temperature was kept at 0 C. throughout the reaction. Adropwise addition of dimethylaniline followed with all of the,B-hydroxypropiohydroxamic acid being dissolved and a colorless solutionobtained.

The reaction mixture was allowed to equilibrate to room temperature andthe excess phosgene was removed at reduced pressure. After washing fourtimes with icewater and drying by filtering through a bed of magnesiumsulfate, the excess solvent was removed and 246 g. (90% yield) of2-(nitrile carbonato) ethyl chloroformate was obtained.

The product was identified by its characteristic LR. absorption at 5.35,5.45 and 562,41, and by elemental analysis:

Calculated: C, 31.10%; H, 2.10%; N, 7.2%; Cl, 18.3%. Obtained: C,31.27%; H, 2.45%; N, 6.45%; Cl, 18.5%.

(C) Preparation of acrylo nitrile carbonate.A 2-liter, fluted, roundbottom flask equipped with stirrer, condenser, dropping funnel andthermometer, containing 233 g. (1.2 moles) of 2-(nitrile carbonato)ethyl chlorofor-mate and 2.33 g. of p-methoxyphenol as an inhibitor, wastreated with 109.7 g. (1.08 moles) of triethyl amine. The addition wascarried out dropwise and at room temperature. The reaction mixture wasthen allowed to stand for several hours and was then washed withice-water (3 times), dried over magnesium sulfate and distilled atreduced pressure to yield a liquid product having a boiling point of 51C. at 4 mm. Hg pressure. The product, 85 g. of which were obtained (69%yield), was identified 9 by the characteristic IR. absorption of 5.35,5.45 and 9.65 and by elemental analysis:

Calculated: C, 42.48%; H, 2.65%. Obtained: C, 42.50%; H, 2.90%.

EXAMPLE V Preparation of homopolymer of acrylonitrile carbonate A yieldof the liquid monomer obtained in Example IV was allowed to stand in acapped bottle for several months to effect polymerization. The mixturewas extracted with pentane to remove unreacted monomer. There resulted54% of a homopolymer of acrylonitrile carbonate, M.P. less than 200 C.(decomposed). The infrared spectrum (Nujol mull) of the homopolymershowed the typical carbonate absorptions. The polymer gave the followingdata upon analysis:

Calc.: C, 42.49%; H, 2.67%; N, 12.39%. Found: C. 42.51%; H, 3.06%; N,12.70%.

EXAMPLE VI.

Preparation of p-vinylbenzonitrile sulfite-styrene copolymer of of A 200cc. pressure bottle was charged with 1.5 g. p-vinylbenzonitrile sulfite,28.5 g. of styrene, 1.5 g. azoisobutyronitrile (AIBN), as initiator, and60 g. of benzene. The system was purged with nitrogen for 10 minutes.The bottle was sealed and placed in a Launderometer at 50 C. and turnedfor forty hours. The reaction mixture was transferred to a suction flaskand the benzene removed under reduced pressure. The polymer wastriturated four times with 250 cc. portions of pentane. There wasobtained 21.0 g. (70%) of copolymer.

AnaIysis.Calc. for of C H NO S and 95% of C H C, 80.61; H, 6.49; N,1.91; O, 6.58; S, 4.39. Found: C, 83.46; H, 6.77; N, 2.37; S, 1.92.

The infrared spectrum of the copolymer (Nujol mull) showed a strongisocyanate peak and no nitrile sulfite absorptions.

EXAMPLE VII Preparation of p-vinylbenzonitrile oxalate-styrene copolymerAnalysis: Calc. for 5% of C H NO and 95% of C H C, 90.66 H, 7.51; N,0.33; O, 88.72; H, 7.70; N, 0.73.

The infrared spectrum of the copolymer (NujoP 1.50. Found: C,

mull) showed the typical nitrile oxalate absorptions. A

sample of the copolymer was heated to boiling for one minute ino-dichlorobenzene and the infrared spectrum of the resulting solutionshowed the disappearance of nitrile oxalate peaks and the appearance ofa strong isocyanate band.

EXAMPLE VIII Preparation of p-vinylbenzonitrile carbonate-styrenecopolymer In a similar manner, 1.5 g. of p-vinylbenzonitrile carbonate,28.5 g. of styrene, 1.5 g. of AIBN and 60 g. of

benzene were charged to a 200 cc. pressure bottle and EXAMPLE IXCopolymerization of acrylonitrile carbonate and styrene To a solution of20.8 g. (0.2 mole) of styrene (inhibitor free) and 4.5 g. (0.4 mole) offreshly distilled acrylonitrile carbonate and 9 g. of anhydrous benzenewas added 0.27 g. of AIBN initiator in a 200 ml. pressure bottle. Thebottle was sealed and agitated at 50 C. for 21 hours. Work-up of theresulting mixture yielded 11.5 g. of a white solid. An IR spectrum ofthe solid in chloroform showed a strong absorption at 5.4-5.5,u,characteristic of the nitrile carbonate group.

Elemental analysis.-Percent C, 75.56; percent H, 6.33; percent N, 4.2.

EXAMPLE X Preparation of p-vinylbenzonitrile oxalate-acrylic acidstyreneterpolymer Using the same procedure, 2.00 g. (0.0092 mole) ofp-vinylbenzonitrile oxalate, 0.66 g. (0.0092 mole) of acrylic acid,27.34 g. (0.26 mole) of styrene, 1.50 g. AIBN and 60.0 g. of benzenewere placed in a 200 cc. pressure bottle and turned for twenty hours at50 C. There was obtained 16.0 g. (52%) of terpolymer, M.P. 129-139 C.

Analysis-Calc. for 3.3% (mole) of C11H7NO4, 3.3% mole) of C H O and93.4% (mole) of C H C, 89.21; H, 7.39; N, 0.43; O, 2.97. Found: C,85.37; H, 7.53; N, 0.99.

The infrared spectrum of the terpolymer (Nujol mull) showed carboxylpeaks and nitrile oxalate absorptions.

Examination of the data obtained in Examples V through VIII disclosesthat there is no interference of the nitrile cyclic structures with freeradical polymerization. Secondly, the infrared spectra of the polymersreveal that only the cyclic nitrile sulfite structure failed to surviveunder the conditions of the polymerization reaction uti lized. This factsuggests that the nitrile sulfite structure is less thermally stablethan the corresponding oxalates and carbonates, and that employing a lowtemperature polymerization may produce a stable sulfite copolymer.

EXAMPLE XI Preparation of fumaronitrile dicarbonate To a 3-liter fluted,round bottom flask equipped with a Dry Ice reflux condenser were added182.6 g. (1.25 moles) of fumarodihydroxamic acid and 500 cc. oftetrahydrofuran (THE). A two-fold excess of phosgene was fed into thereaction mixture over a period of about two hours and the temperature ofthe reaction was maintained at about room temperature. The reactionmixture was allowed to stand overnight, whereupon the product wasseparated from unreacted starting material. There resulted a 66.9% yieldof recrystallized (from toluene) fumaronitrile dicarbonate, M.P. 163-165C. Yield of product is based on reacted starting material.

The infrared spectrum (Nujol mull) of the product showed the typicalnitrile carbonate absorptions. The product gave the following data uponanalysis:

Calculated: C, 36.38%; H, 1.02%; N, 14.14%. Found: C, 36.70%;H, 1.42%;N, 12.63%.

EXAMPLE XII Preparation of fumaronitrile disulfite To a 300 cc. fluted,round bottom flask equipped with a reflux condenser attached to a CaCldrying tube were added 4.2 g. (0.029 mole) of fumarodihydroxamic acidand 248 g. (2.08 moles) of thionyl chloride. The reaction mixture wasstirred mechanically and heated to reflux for half an hour. Theresulting solution was filtered and the thionyl chloride removed underreduced pressure. There resulted a quantitative yield of crudefumaronitrile disulfite, M.P. 149l50 C. (decomposed). Recrystallizationfrom benzene gave white needles, M.P. 150 C. (decomposed). The infraredspectrum (NujoP mull) of the recrystallized material showed the typicalcyclic nitrile sulfite absorptions.

The product gave the following data upon analysis:

Calculated: C, 20.20%; H, 0.84%; N, 11.80%. Found: C, 21.70%; H, 1.25%;N, 13.90%.

It is claimed:

1. An addition polymer of:

(a) about 1 to 100 weight percent of an ethylenicallyunsaturated, cyclicnitrile adduct having the general radicals, x is or 1, and Y is anethylenicallyunsaturated hydrocarbon group of 2 to about 20 carbonatoms, and (b) about 0 to 99 weight percent of a dissimilar, additionpolymerizable, ethylenically unsaturated monomer of 2 to about 20 carbonatoms, said dissimilar monomer being devoid of groups which are reactivewith the cyclic nitrile group of said adduct under additionpolymerization conditions, and said polymer having a molecular weight ofat least about 250. 2. The addition polymer of claim 1 wherein thecyclic nitrile adduct is acrylonitrile carbonate having the structuralformula:

0H2=GHb 1 I 3. The addition polymer of claim 2 having a molecular weightof about 750 to 500,000.

4. The addition polymer of claim 3 wherein the dissimilar,ethylenically-unsaturated monomer is vinylaromatic hydrocarbon.

5. The addition polymer of claim 4 containing about 5 to 25 weightpercent of polymerized acrylonitrile carbonate and about to weightpercent of polymerized vinylaromatic hydrocarbon.

6. The addition polymer of claim 1 wherein X is II C 11. The additionpolymer of claim 10 wherein the dissimilar monomer is styrene.

12. The addition polymer of claim 9 wherein the cyclic nitrile adduct isp-vinylbenzonitrile oxalate having the structural formula:

I ll

13. The addition polymer of claim 12 wherein the dissimilar monomer isstyrene.

References Cited UNITED STATES PATENTS 8/1966 Burk et al 260301 OTHERREFERENCES Beck: Chemical Abstracts, vol. 46 (1952), col. 3046-7.

Bykhovskaya et al.: Chemical Abstracts, vol. 54 (1960), col. 259-260.

Farbwerke Hoechst, Chemical Abstracts, vol. (1962), col. 5931 (Abstractof German 1,125,931).

Buyle et al.: Chemical Abstracts, vol. 59 (1963), col. 5167-8.

SAMUEL H. BLECH, Primary Examiner U.S. Cl. X.R.

